Stabilizing Voltage And Prolonged Cycling Life Of Li-Rich Mn-Based Oxides Through Spinel "Lithium Ion Pump" Heteroepitaxial Coating Strategy

The practical application of Li-rich layered oxides is impeded by its cycle instability, poor rate capability and serious voltage decay. Here, nano-sized spinel Li4Ti5O12 (LTO) is constructed on Li1.2Ni0.13Co0.13Mn0.54O2 (LLNCMO). The distinctly heteroepitaxial structure of LTO nanocoating on LLNCMO is corroborated by HAADF-STEM. The LTO coating with fast lithium ion diffusion kinetics acts as "lithium ion pump" when Li+-ions cross over it. The integrated structure can effectively retard oxygen evolution and phase transformation engendering higher capacity and voltage retention. LTO heteroepitaxially coated LLNCMO (LTO@LLNCMO) shows an improvement of initial coulombic efficiency to 74.3% and more stable life with a high capacity retention up to 96.9% at 2C after 500 cycles (40.5% for LLNCMO). LTO@LLNCMO demonstrates minimal voltage fading of 1.33 mV per cycle suggesting suppression of phase conversion to spinel-like structure. The epitaxial spinel modification strategy can be applied to control the surface stability of cathodes. (C) 2021 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.